RESUMO
We survey some obstacles that a chemist encounters in defining conditions for radiation chemical experiments relevant to cometary nuclei. The choice of working conditions is examined in the light to present knowledge about comets and the facilities available for routine work in radiation chemistry.
Assuntos
Meteoroides , Radioquímica , Radiação Cósmica , Gelo , Transferência Linear de Energia , PrótonsRESUMO
The behavior of an aqueous-dominant multicomponent cometary model is examined at high doses of ionizing radiation. The system is composed of a water mixture of HCN (0.2 mol dm-3), CH3CN (0.04 mol dm-3), C2H5CN (0.02 mol dm-3), CH3OH (0.12 mol dm-3) and HCO2H (0.01 mol dm-3. It was exposed to gamma rays at doses up to 18.5 MGy. The chemical kinetic database used in the computer treatment of experimental data consists of 79 reactions. A complex mixture of products has been synthesized: gases, amino acids, carboxylic acids and polymeric material. The results suggest that the pristine material in cometary nuclei may have been chemically altered by the action of cosmic rays and embedded radionuclides.
Assuntos
Aminoácidos/síntese química , Ácidos Carboxílicos/síntese química , Raios gama , Gases/síntese química , Meteoroides , Polímeros/síntese química , Bases de Dados Factuais , Formiatos/química , Formiatos/efeitos da radiação , Hidrocarbonetos/síntese química , Cianeto de Hidrogênio/química , Cianeto de Hidrogênio/efeitos da radiação , Metanol/química , Metanol/efeitos da radiação , Modelos Químicos , Nitrilas/química , Nitrilas/efeitos da radiação , Radioquímica , Água/químicaRESUMO
Oligomers formed by ionizing radiation in aqueous cyanide solutions, under various experimental conditions, have been characterized by infrared spectroscopy. IR bands appear in the region known to be characteristic for amides and peptides. The results are discussed in relation to radiation-induced formation of peptidic material and the potential role of ionizing radiation as an energy source for some processes in prebiotic molecular evolution.
Assuntos
Cianetos/efeitos da radiação , Peptídeos , Relação Dose-Resposta à Radiação , Raios gama , Peptídeos/síntese química , Soluções , Espectrofotometria Infravermelho , ÁguaRESUMO
Oxygen-free aqueous solutions of NH4CN (0.1 M, pH9) were exposed to gamma rays from a 60Co source, the mixture of nonvolatile products was fractionated, and the fractions were analyzed. The procedures were chosen to make effective investigations of radiolytic products, and to minimize the contributions of chemical changes which are known to occur in aqueous solution in the absence of ionizing radiation. It has been found that the main constituents are: urea, 25.9%; an oligomer, very likely oligoimine (18.4%); and several fractions (about 50%) which release amino acids on hydrolysis. These fractions differ considerably, as shown by amino acid assay, enzymatic digestion, IR spectra, and biuret reaction. All these tests were found to be positive for two fractions; in two further fractions the enzymatic cleavage was absent, but other tests were positive. Negative enzymatic and biuret tests, and no bands characteristic of amide or peptide, were found for a fraction whose hydrolysate consisted of 55% glycine. Although most of the isolated materials were found to be composite, the results of the analyses were sufficient for getting a reliable over-all picture of the chemical action of the ionizing radiation. The role of free radicals in reactions leading to the formations of radiolytic products was considered.
Assuntos
Cianetos/efeitos da radiação , Compostos de Amônio Quaternário/efeitos da radiação , Aminoácidos/análise , Aminopeptidases , Evolução Biológica , Fracionamento Químico/métodos , Radioisótopos de Cobalto , Raios gama , Oligopeptídeos/análise , Pronase , Espectrofotometria Infravermelho , Ureia/análiseRESUMO
Oxygen-free aqueous solutions of CH3CN (0.1 M, pH 6) were exposed to gamma rays from a 60Co source, the mixture of nonvolatile radiolytic products was fractionated and the fractions were analysed. Succinic, maleic, fumaric, malonic and pyruvic acids were identified. Glycol aldehyde, glucose and probably ribose were observed in the hydrolysate of fractionated material. It has been suggested that an oligomer is formed which has a fragment with the polyhydroxy structure and on hydrolysis releases the carbohydrates. Radiolytic products which release amino acids on hydrolysis were found in several fractions. The amino acid contents of the hydrolysates were up to about 2.8% of the fraction mass. The presence of several protein and nonprotein amino acids suggests that their origin should be in a peptidic structure, which is probably a fragment of an oligomer radiolytically produced. A direct analysis of the irradiated solution shows the presence of acetaldehyde, propionaldehyde, glyoxal and of biacetyl. Experimental findings are discussed and a free-radical mechanism is proposed to account for the chemical changes observed.
Assuntos
Acetonitrilas/efeitos da radiação , Acetonitrilas/análise , Aldeídos/análise , Aminoácidos/análise , Evolução Biológica , Carboidratos/análise , Ácidos Carboxílicos/análise , Fracionamento Químico/métodos , Radioisótopos de Cobalto , Raios gama , Espectrofotometria InfravermelhoRESUMO
We have examined a water-dominated multicomponent system after irradiation in the multimegarad dose range with gamma rays from a 60Co source at both 77 and 310 K. The constituents were simple organic compounds in the proportions in which they appear in a dense interstellar cloud: HCN/CH3OH/CH3CN/C2H5CN/HCOOH = 1:0.6:0.2:0.1:0.05. The total amounts were adjusted to correspond to a carbon to nitrogen ratio of 1.8 and a water content of about 50% in a cometary nucleus where the dust to volatiles ratio is 1; the total amount of CN-bearing compounds was taken to correspond to 0.4% of the cometary mass. In experiments at 310 K about 40 radiolytic products are identified, among them aldehydes and amino and carboxylic acids. Abundant polymeric material (Mw up to 80,000 daltons) is formed. The basic aspects of radiolysis of the liquid system are present also at 77 K, although at radiation-chemical yields that are lower by one to two orders of magnitude. We have considered the relevance of the present findings to the chemistry of a liquid-water core and the icy layers of a cometary nucleus.